US20090172895A1

US20090172895A1 - Enzyme and fabric hueing agent containing compositions

Info

Publication number: US20090172895A1
Application number: US12/341,708
Authority: US
Inventors: Neil Joseph Lant; Eugene Steven Sadlowski; Genevieve Cagalawan Wenning
Original assignee: Procter and Gamble Co
Current assignee: Procter and Gamble Co
Priority date: 2008-01-04
Filing date: 2008-12-22
Publication date: 2009-07-09
Also published as: JP5405488B2; US8512418B2; PL2242830T3; CN101910392A; ZA201004547B; EP2242830A1; RU2470070C2; JP2011511099A; CA2709609C; ES2412683T3; CA2709609A1; WO2009087524A1; EG25965A; EP2242830B2; CN101910392B; BRPI0822220A2; RU2010125315A; AR070102A1; ES2412683T5; EP2242830B1

Abstract

This invention relates to compositions comprising certain glycosyl hydrolases and a fabric hueing agent and processes for making and using such compositions.

Description

CROSS REFERENCE TO RELATED APPLICATIONS

This application claims the benefit of U.S. Provisional Application No. 61/009,982 filed 4 Jan. 2008; and U.S. Provisional Application No. 61/114,599 filed 14 Nov. 2008.

FIELD OF INVENTION

This invention relates to compositions comprising certain glycosyl hydrolases and fabric hueing agents.

BACKGROUND OF THE INVENTION

Detergent manufacturers incorporate hueing agents into their laundry detergent products to impart visual fabric benefits to fabric laundered therewith. However, it has proven difficult to deliver adequate consumer acceptable visual benefits and there remains a need to improve the fabric hueing profile of these laundry detergent compositions. The Inventors have found that additionally incorporating certain glycosyl hydrolases into a laundry detergent composition that comprises a hueing agent, improves the whiteness perception and hueing profile of the composition. Without wishing to be bound by theory, the Inventors believe that these glycosyl hyrolases biopolish the fabric surface in such a manner so as to improve the deposition and the performance of the hueing agents.

SUMMARY OF THE INVENTION

This invention relates to compositions comprising certain glycosyl hydrolases and fabric hueing agents and processes for making and using such products.

DETAILED DESCRIPTION OF THE INVENTION

Laundry Detergent Composition

The laundry detergent composition typically comprises from about 0.00003 wt % to about 0.1 wt %, from about 0.00008 wt % to about 0.05 wt %, or even from about 0.0001 wt % to about 0.04 wt %, fabric hueing agent and from about 0.0005 wt % to about 0.1 wt %, from about 0.001 wt % to about 0.05 wt %, or even from about 0.002 wt % to about 0.03 wt % glycosyl hydrolase. The balance of any aspects of the aforementioned composition is made up of one or more adjunct materials. The fabric hueing agent and glycosyl hydrolase are described in more detail below.
The composition may take any form, but preferably the composition is in the form of a liquid. The composition may be in the form of a unit dose pouch, especially when in the form of a liquid, and typically the composition is at least partially, preferably completely, enclosed by a water-soluble pouch.
Solid Laundry Detergent Composition
In one embodiment of the present invention, the composition is a solid laundry detergent composition, preferably a solid laundry powder detergent composition.
The composition preferably comprises from 0 wt % to 10 wt %, or even to 5 wt % zeolite builder. The composition also preferably comprises from 0 wt % to 10 wt %, or even to 5 wt % phosphate builder.
The composition typically comprises anionic detersive surfactant, preferably linear alkyl benzene sulphonate, preferably in combination with a co-surfactant. Preferred co-surfactants are alkyl ethoxylated sulphates having an average degree of ethoxylation of from 1 to 10, preferably from 1 to 3, and/or ethoxylated alcohols having an average degree of ethoxylation of from 1 to 10, preferably from 3 to 7.
The composition preferably comprises chelant, preferably the composition comprises from 0.3 wt % to 2.0 wt % chelant. A suitable chelant is ethylenediamine-N,N′-disuccinic acid (EDDS).
The composition may comprise cellulose polymers, such as sodium or potassium salts of carboxymethyl cellulose, carboxyethyl cellulose, sulfoethyl cellulose, sulfopropyl cellulose, cellulose sulfate, phosphorylated cellulose, carboxymethyl hydroxyethyl cellulose, carboxymethyl hydroxypropyl cellulose, sulfoethyl hydroxyethyl cellulose, sulfoethyl hydroxypropyl cellulose, carboxymethyl methyl hydroxyethyl cellulose, carboxymethyl methyl cellulose, sulfoethyl methyl hydroxyethyl cellulose, sulfoethyl methyl cellulose, carboxymethyl ethyl hydroxyethyl cellulose, carboxymethyl ethyl cellulose, sulfoethyl ethyl hydroxyethyl cellulose, sulfoethyl ethyl cellulose, carboxymethyl methyl hydroxypropyl cellulose, sulfoethyl methyl hydroxypropyl cellulose, carboxymethyl dodecyl cellulose, carboxymethyl dodecoyl cellulose, carboxymethyl cyanoethyl cellulose, and sulfoethyl cyanoethyl cellulose. The cellulose may be a substituted cellulose substituted by two or more different substituents, such as methyl and hydroxyethyl cellulose.
The composition may comprise soil release polymers, such as Repel-o-Tex™. Other suitable soil release polymers are anionic soil release polymers. Suitable soil release polymers are described in more detail in WO05123835A1, WO07079850A1 and WO08110318A2.
The composition may comprise a spray-dried powder. The spray-dried powder may comprise a silicate salt, such as sodium silicate.

Glycosyl Hydrolase

The glycosyl hydrolase has enzymatic activity towards both xyloglucan and amorphous cellulose substrates, wherein the glycosyl hydrolase is selected from GH families 5, 12, 44 or 74.
The enzymatic activity towards xyloglucan substrates is described in more detail below. The enzymatic activity towards amorphous cellulose substrates is described in more detail below.
The glycosyl hydrolase enzyme preferably belongs to glycosyl hydrolase family 44. The glycosyl hydrolase (GH) family definition is described in more detail in Biochem J. 1991, v280, 309-316.
The glycosyl hydrolase enzyme preferably has a sequence at least 70%, or at least 75% or at least 80%, or at least 85%, or at least 90%, or at least 95% identical to sequence ID No. 1.
For purposes of the present invention, the degree of identity between two amino acid sequences is determined using the Needleman-Wunsch algorithm (Needleman and Wunsch, 1970, J. Mol. Biol. 48: 443-453) as implemented in the Needle program of the EMBOSS package (EMBOSS: The European Molecular Biology Open Software Suite, Rice et al., 2000, Trends in Genetics 16: 276-277), preferably version 3.0.0 or later. The optional parameters used are gap open penalty of 10, gap extension penalty of 0.5, and the EBLOSUM62 (EMBOSS version of BLOSUM62) substitution matrix. The output of Needle labeled “longest identity” (obtained using the—no brief option) is used as the percent identity and is calculated as follows: (Identical Residues×100)/(Length of Alignment−Total Number of Gaps in Alignment).
Suitable glycosyl hydrolases are selected from the group consisting of: GH family 44 glycosyl hydrolases from Paenibacillus polyxyma (wild-type) such as XYG1006 described in WO 01/062903 or are variants thereof, GH family 12 glycosyl hydrolases from Bacillus licheniformis (wild-type) such as Seq. No. ID: 1 described in WO 99/02663 or are variants thereof, GH family 5 glycosyl hydrolases from Bacillus agaradhaerens (wild type) or variants thereof, GH family 5 glycosyl hydrolases from Paenibacillus (wild type) such as XYG1034 and XYG 1022described in WO 01/064853 or variants thereof, GH family 74 glycosyl hydrolases from Jonesia sp. (wild type) such as XYG1020 described in WO 2002/077242 or variants thereof, and GH family 74 glycosyl hydrolases from Trichoderma Reesei (wild type), such as the enzyme described in more detail in Sequence ID no. 2 of WO03/089598, or variants thereof.
Preferred glycosyl hydrolases are selected from the group consisting of: GH family 44 glycosyl hydrolases from Paenibacillus polyxyma (wild-type) such as XYG1006 or are variants thereof

Enzymatic Activity Towards Xyloglucan Substrates

An enzyme is deemed to have activity towards xyloglucan if the pure enzyme has a specific activity of greater than 50000 XyloU/g according to the following assay at pH 7.5.
The xyloglucanase activity is measured using AZCL-xyloglucan from Megazyme, Ireland as substrate (blue substrate).
A solution of 0.2% of the blue substrate is suspended in a 0.1M phosphate buffer pH 7.5, 20° C. under stirring in a 1.5 ml Eppendorf tubes (0.75 ml to each), 50 microlitres enzyme solution is added and they are incubated in an Eppendorf Thermomixer for 20 minutes at 40° C., with a mixing of 1200 rpm. After incubation the coloured solution is separated from the solid by 4 minutes centrifugation at 14,000 rpm and the absorbance of the supernatant is measured at 600 nm in a 1 cm cuvette using a spectrophotometer. One XyloU unit is defined as the amount of enzyme resulting in an absorbance of 0.24 in a 1 cm cuvette at 600 nm.
Only absorbance values between 0.1 and 0.8 are used to calculate the XyloU activity. If an absorbance value is measured outside this range, optimization of the starting enzyme concentration should be carried out accordingly.

Enzymatic Activity Towards Amorphous Cellulose Substrates

An enzyme is deemed to have activity towards amorphous cellulose if the pure enzyme has a specific activity of greater than 20000 EBG/g according to the following assay at pH 7.5. Chemicals used as buffers and substrates were commercial products of at least reagent grade.

Endoglucanase Activity Assay Materials:

0.1 M phosphate buffer pH 7.5
Cellazyme C tablets, supplied by Megazyme International, Ireland.
Glass microfiber filters, GF/C, 9 cm diameter, supplied by Whatman.

Method:

In test tubes, mix 1 ml pH 7,5 buffer and 5 ml deionised water.
Add 100 microliter of the enzyme sample (or of dilutions of the enzyme sample with known weight:weight dilution factor). Add 1 Cellazyme C tablet into each tube, cap the tubes and mix on a vortex mixer for 10 seconds. Place the tubes in a thermostated water bath, temperature 40° C..
After 15, 30 and 45 minutes, mix the contents of the tubes by inverting the tubes, and replace in the water bath. After 60 minutes, mix the contents of the tubes by inversion and then filter through a GF/C filter. Collect the filtrate in a clean tubes.
Measure Absorbance (Aenz) at 590 nm, with a spectrophotometer. A blank value, Awater, is determined by adding 100 μl water instead of 100 microliter enzyme dilution.
Calculate Adelta=Aenz−Awater.
Adelta must be <0.5. If higher results are obtained, repeat with a different enzyme dilution factor.
Determine DFO.1, where DFO.1 is the dilution factor needed to give Adelta=0.1.
Unit Definition: 1 Endo-Beta-Glucanase activity unit (1 EBG) is the amount of enzyme that gives Adelta=0.10, under the assay conditions specified above. Thus, for example, if a given enzyme sample, after dilution by a dilution factor of 100, gives Adelta=0. 0, then the enzyme sample has an activity of 100 EBG/g.

Suitable Fabric Hueing Agents

Fluorescent optical brighteners emit at least some visible light. In contrast, fabric hueing agents can alter the tint of a surface as they absorb at least a portion of the visible light spectrum. Suitable fabric hueing agents include dyes, dye-clay conjugates, and pigments that satisfy the requirements of Test Method 1 in the Test Method Section of the present specification. Suitable dyes include small molecule dyes and polymeric dyes. Suitable small molecule dyes include small molecule dyes selected from the group consisting of dyes falling into the Colour Index (C.I.) classifications of Direct Blue, Direct Red, Direct Violet, Acid Blue, Acid Red, Acid Violet, Basic Blue, Basic Violet and Basic Red, or mixtures thereof, for example:

(1) Tris-azo direct blue dyes of the formula

where at least two of the A, B and C napthyl rings are substituted by a sulfonate group, the C ring may be substituted at the 5 position by an NH₂or NHPh group, X is a benzyl or naphthyl ring substituted with up to 2 sulfonate groups and may be substituted at the 2 position with an OH group and may also be substituted with an NH₂or NHPh group.

(2) bis-azo Direct violet dyes of the formula:

where Z is H or phenyl, the A ring is preferably substituted by a methyl and methoxy group at the positions indicated by arrows, the A ring may also be a naphthyl ring, the Y group is a benzyl or naphthyl ring, which is substituted by sulfate group and may be mono or disubstituted by methyl groups.

(3) Blue or red acid dyes of the formula

where at least one of X and Y must be an aromatic group. In one aspect, both the aromatic groups may be a substituted benzyl or naphthyl group, which may be substituted with non water-solubilising groups such as alkyl or alkyloxy or aryloxy groups, X and Y may not be substituted with water solubilising groups such as sulfonates or carboxylates. In another aspect, X is a nitro substituted benzyl group and Y is a benzyl group

(4) Red acid dyes of the structure

where B is a naphthyl or benzyl group that may be substituted with non water solubilising groups such as alkyl or alkyloxy or aryloxy groups, B may not be substituted with water solubilising groups such as sulfonates or carboxylates.

(5) Dis-azo dyes of the structure

wherein X and Y, independently of one another, are each hydrogen, C₁-C₄alkyl or C₁-C₄-alkoxy, Rα is hydrogen or aryl, Z is C₁-C₄alkyl; C₁C₄-alkoxy; halogen; hydroxyl or carboxyl, n is 1 or 2 and m is 0, 1 or 2, as well as corresponding salts thereof and mixtures thereof

(6) Triphenylmethane dyes of the following structures

and mixtures thereof. In another aspect, suitable small molecule dyes include small molecule dyes selected from the group consisting of Colour Index (Society of Dyers and Colourists, Bradford, UK) numbers Direct Violet 9, Direct Violet 35, Direct Violet 48, Direct Violet 51, Direct Violet 66, Direct Blue 1, Direct Blue 71, Direct Blue 80, Direct Blue 279, Acid Red 17, Acid Red 73, Acid Red 88, Acid Red 150, Acid Violet 15, Acid Violet 17, Acid Violet 24, Acid Violet 43, Acid Red 52, Acid Violet 49, Acid Blue 15, Acid Blue 17, Acid Blue 25, Acid Blue 29, Acid Blue 40, Acid Blue 45, Acid Blue 75, Acid Blue 80, Acid Blue 83, Acid Blue 90 and Acid Blue 113, Acid Black 1, Basic Violet 1, Basic Violet 3, Basic Violet 4, Basic Violet 10, Basic Violet 35, Basic Blue 3, Basic Blue 16, Basic Blue 22, Basic Blue 47, Basic Blue 66, Basic Blue 75, Basic Blue 159 and mixtures thereof. In another aspect, suitable small molecule dyes include small molecule dyes selected from the group consisting of Colour Index (Society of Dyers and Colourists, Bradford, UK) numbers Acid Violet 17, Acid Violet 43, Acid Red 52, Acid Red 73, Acid Red 88, Acid Red 150, Acid Blue 25, Acid Blue 29, Acid Blue 45, Acid Blue 113, Acid Black 1, Direct Blue 1, Direct Blue 71, Direct Violet 51 and mixtures thereof. In another aspect, suitable small molecule dyes include small molecule dyes selected from the group consisting of Colour Index (Society of Dyers and Colourists, Bradford, UK) numbers Acid Violet 17, Direct Blue 71, Direct Violet 51, Direct Blue 1, Acid Red 88, Acid Red 150, Acid Blue 29, Acid Blue 113 or mixtures thereof.
Suitable polymeric dyes include polymeric dyes selected from the group consisting of polymers containing conjugated chromogens (dye-polymer conjugates) and polymers with chromogens co-polymerized into the backbone of the polymer and mixtures thereof
In another aspect, suitable polymeric dyes include polymeric dyes selected from the group consisting of fabric-substantive colorants sold under the name of Liquitint® (Milliken, Spartanburg, S.C., USA), dye-polymer conjugates formed from at least one reactive dye and a polymer selected from the group consisting of polymers comprising a moiety selected from the group consisting of a hydroxyl moiety, a primary amine moiety, a secondary amine moiety, a thiol moiety and mixtures thereof. In still another aspect, suitable polymeric dyes include polymeric dyes selected from the group consisting of Liquitint® (Milliken, Spartanburg, S.C., USA) Violet CT, carboxymethyl cellulose (CMC) conjugated with a reactive blue, reactive violet or reactive red dye such as CMC conjugated with C.I. Reactive Blue 19, sold by Megazyme, Wicklow, Ireland under the product name AZO-CM-CELLULOSE, product code S-ACMC, alkoxylated triphenyl-methane polymeric colourants, alkoxylated thiophene polymeric colourants, and mixtures thereof.
Suitable dye clay conjugates include dye clay conjugates selected from the group comprising at least one cationic/basic dye and a smectite clay, and mixtures thereof. In another aspect, suitable dye clay conjugates include dye clay conjugates selected from the group consisting of one cationic/basic dye selected from the group consisting of C.I. Basic Yellow I through 108, C.I. Basic Orange 1 through 69, C.I. Basic Red 1 through 118, C.I. Basic Violet 1 through 51, C.I. Basic Blue 1 through 164, C.I. Basic Green 1 through 14, C.I. Basic Brown 1 through 23, CI Basic Black 1 through 11, and a clay selected from the group consisting of Montmorillonite clay, Hectorite clay, Saponite clay and mixtures thereof. In still another aspect, suitable dye clay conjugates include dye clay conjugates selected from the group consisting of: Montmorillonite Basic Blue B7 C.I. 42595 conjugate, Montmorillonite Basic Blue B9 C.I. 52015 conjugate, Montmorillonite Basic Violet V3 C.I. 42555 conjugate, Montmorillonite Basic Green G1 C.I. 42040 conjugate, Montmorillonite Basic Red R1 C.I. 45160 conjugate, Montmorillonite C.I. Basic Black 2 conjugate, Hectorite Basic Blue B7 C.I. 42595 conjugate, Hectorite Basic Blue B9 C.I. 52015 conjugate, Hectorite Basic Violet V3 C.I. 42555 conjugate, Hectorite Basic Green G1 C.I. 42040 conjugate, Hectorite Basic Red R1 C.I. 45160 conjugate, Hectorite C.I. Basic Black 2 conjugate, Saponite Basic Blue B7 C.I. 42595 conjugate, Saponite Basic Blue B9 C.I. 52015 conjugate, Saponite Basic Violet V3 C.I. 42555 conjugate, Saponite Basic Green G1 C.I. 42040 conjugate, Saponite Basic Red R1 C.I. 45160 conjugate, Saponite C.I. Basic Black 2 conjugate and mixtures thereof.
Suitable pigments include pigments selected from the group consisting of flavanthrone, indanthrone, chlorinated indanthrone containing from 1 to 4 chlorine atoms, pyranthrone, dichloropyranthrone, monobromodichloropyranthrone, dibromodichloropyranthrone, tetrabromopyranthrone, perylene-3,4,9,10-tetracarboxylic acid diimide, wherein the imide groups may be unsubstituted or substituted by C1-C3-alkyl or a phenyl or heterocyclic radical, and wherein the phenyl and heterocyclic radicals may additionally carry substituents which do not confer solubility in water, anthrapyrimidinecarboxylic acid amides, violanthrone, isoviolanthrone, dioxazine pigments, copper phthalocyanine which may contain up to 2 chlorine atoms per molecule, polychloro-copper phthalocyanine or polybromochloro-copper phthalocyanine containing up to 14 bromine atoms per molecule and mixtures thereof. In another aspect, suitable pigments include pigments selected from the group consisting of Ultramarine Blue (C.I. Pigment Blue 29), Ultramarine Violet (C.I. Pigment Violet 15) and mixtures thereof.
The aforementioned fabric hueing agents can be used in combination (any mixture of fabric hueing agents can be used). Suitable fabric hueing agents can be purchased from Aldrich, Milwaukee, Wis., USA; Ciba Specialty Chemicals, Basel, Switzerland; BASF, Ludwigshafen, Germany; Dayglo Color Corporation, Mumbai, India; Organic Dyestuffs Corp., East Providence, R.I., USA; Dystar, Frankfurt, Germany; Lanxess, Leverkusen, Germany; Megazyme, Wicklow, Ireland; Clariant, Muttenz, Switzerland; Avecia, Manchester, UK and/or made in accordance with the examples contained herein.
Suitable hueing agents are described in more detail in U.S. Pat. No. 7,208,459 B2.

Adjunct Materials

While not essential for the purposes of the present invention, the non-limiting list of adjuncts illustrated hereinafter are suitable for use in the instant compositions and may be desirably incorporated in certain embodiments of the invention, for example to assist or enhance cleaning performance, for treatment of the substrate to be cleaned, or to modify the aesthetics of the cleaning composition as is the case with perfumes, colorants, dyes or the like. The precise nature of these additional components, and levels of incorporation thereof, will depend on the physical form of the composition and the nature of the cleaning operation for which it is to be used. Suitable adjunct materials include, but are not limited to, surfactants, builders, chelating agents, dye transfer inhibiting agents, dispersants, additional enzymes, and enzyme stabilizers, catalytic materials, bleach activators, hydrogen peroxide, sources of hydrogen peroxide, preformed peracids, polymeric dispersing agents, clay soil removal/anti-redeposition agents, brighteners, suds suppressors, dyes, perfumes, structure elasticizing agents, fabric softeners, carriers, hydrotropes, processing aids, solvents and/or pigments. In addition to the disclosure below, suitable examples of such other adjuncts and levels of use are found in U.S. Pat. Nos. 5,576,282, 6,306,812 B1 and 6,326,348 B1 that are incorporated by reference.
As stated, the adjunct ingredients are not essential to Applicants' compositions. Thus, certain embodiments of Applicants' compositions do not contain one or more of the following adjuncts materials: surfactants, builders, chelating agents, dye transfer inhibiting agents, dispersants, additional enzymes, and enzyme stabilizers, catalytic materials, bleach activators, hydrogen peroxide, sources of hydrogen peroxide, preformed peracids, polymeric dispersing agents, clay soil removal/anti-redeposition agents, brighteners, suds suppressors, dyes, perfumes, structure elasticizing agents, fabric softeners, carriers, hydrotropes, processing aids, solvents and/or pigments. However, when one or more adjuncts are present, such one or more adjuncts may be present as detailed below:
Bleaching Agents—The cleaning compositions of the present invention may comprise one or more bleaching agents. Suitable bleaching agents other than bleaching catalysts include photobleaches, bleach activators, hydrogen peroxide, sources of hydrogen peroxide, pre-formed peracids and mixtures thereof. In general, when a bleaching agent is used, the compositions of the present invention may comprise from about 0.1% to about 50% or even from about 0.1% to about 25% bleaching agent by weight of the subject cleaning composition. Examples of suitable bleaching agents include:
(1) photobleaches for example sulfonated zinc phthalocyanine sulfonated aluminium phthalocyanines, xanthene dyes and mixtures thereof;
(2) preformed peracids: Suitable preformed peracids include, but are not limited to, compounds selected from the group consisting of percarboxylic acids and salts, percarbonic acids and salts, perimidic acids and salts, peroxymonosulfuric acids and salts, for example, Oxone®, and mixtures thereof. Suitable percarboxylic acids include hydrophobic and hydrophilic peracids having the formula R—(C═O)O—O-M wherein R is an alkyl group, optionally branched, having, when the peracid is hydrophobic, from 6 to 14 carbon atoms, or from 8 to 12 carbon atoms and, when the peracid is hydrophilic, less than 6 carbon atoms or even less than 4 carbon atoms; and M is a counterion, for example, sodium, potassium or hydrogen;
(3) sources of hydrogen peroxide, for example, inorganic perhydrate salts, including alkali metal salts such as sodium salts of perborate (usually mono- or tetra-hydrate), percarbonate, persulphate, perphosphate, persilicate salts and mixtures thereof. In one aspect of the invention the inorganic perhydrate salts are selected from the group consisting of sodium salts of perborate, percarbonate and mixtures thereof. When employed, inorganic perhydrate salts are typically present in amounts of from 0.05 to 40 wt %, or 1 to 30 wt % of the overall composition and are typically incorporated into such compositions as a crystalline solid that may be coated. Suitable coatings include, inorganic salts such as alkali metal silicate, carbonate or borate salts or mixtures thereof, or organic materials such as water-soluble or dispersible polymers, waxes, oils or fatty soaps; and
(4) bleach activators having R—(C═O)-L wherein R is an alkyl group, optionally branched, having, when the bleach activator is hydrophobic, from 6 to 14 carbon atoms, or from 8 to 12 carbon atoms and, when the bleach activator is hydrophilic, less than 6 carbon atoms or even less than 4 carbon atoms; and L is leaving group. Examples of suitable leaving groups are benzoic acid and derivatives thereof—especially benzene sulphonate. Suitable bleach activators include dodecanoyl oxybenzene sulphonate, decanoyl oxybenzene sulphonate, decanoyl oxybenzoic acid or salts thereof, 3,5,5-trimethyl hexanoyloxybenzene sulphonate, tetraacetyl ethylene diamine (TAED) and nonanoyloxybenzene sulphonate (NOBS). Suitable bleach activators are also disclosed in WO 98/17767. While any suitable bleach activator may be employed, in one aspect of the invention the subject cleaning composition may comprise NOBS, TAED or mixtures thereof
When present, the peracid and/or bleach activator is generally present in the composition in an amount of from about 0.1 to about 60 wt %, from about 0.5 to about 40 wt % or even from about 0.6 to about 10 wt % based on the composition. One or more hydrophobic peracids or precursors thereof may be used in combination with one or more hydrophilic peracid or precursor thereof.
The amounts of hydrogen peroxide source and peracid or bleach activator may be selected such that the molar ratio of available oxygen (from the peroxide source) to peracid is from 1:1 to 35: 1, or even 2:1 to 10:1.
Surfactants—The cleaning compositions according to the present invention may comprise a surfactant or surfactant system wherein the surfactant can be selected from nonionic surfactants, anionic surfactants, cationic surfactants, ampholytic surfactants, zwitterionic surfactants, semi-polar nonionic surfactants and mixtures thereof When present, surfactant is typically present at a level of from about 0.1% to about 60%, from about 1% to about 50% or even from about 5% to about 40% by weight of the subject composition.
Builders—The cleaning compositions of the present invention may comprise one or more detergent builders or builder systems. When a builder is used, the subject composition will typically comprise at least about 1%, from about 5% to about 60% or even from about 10% to about 40% builder by weight of the subject composition.
Builders include, but are not limited to, the alkali metal, ammonium and alkanolammonium salts of polyphosphates, alkali metal silicates, alkaline earth and alkali metal carbonates, aluminosilicate builders and polycarboxylate compounds, ether hydroxypolycarboxylates, copolymers of maleic anhydride with ethylene or vinyl methyl ether, 1,3,5-trihydroxy benzene-2,4,6-trisulphonic acid, and carboxymethyloxysuccinic acid, the various alkali metal, ammonium and substituted ammonium salts of polyacetic acids such as ethylenediamine tetraacetic acid and nitrilotriacetic acid, as well as polycarboxylates such as mellitic acid, succinic acid, citric acid, oxydisuccinic acid, polymaleic acid, benzene 1,3,5-tricarboxylic acid, carboxymethyloxysuccinic acid, and soluble salts thereof.
Chelating Agents—The cleaning compositions herein may contain a chelating agent. Suitable chelating agents include copper, iron and/or manganese chelating agents and mixtures thereof When a chelating agent is used, the subject composition may comprise from about 0.005% to about 15% or even from about 3.0% to about 10% chelating agent by weight of the subject composition.
Dye Transfer Inhibiting Agents—The cleaning compositions of the present invention may also include one or more dye transfer inhibiting agents. Suitable polymeric dye transfer inhibiting agents include, but are not limited to, polyvinylpyrrolidone polymers, polyamine N-oxide polymers, copolymers of N-vinylpyrrolidone and N-vinylimidazole, polyvinyloxazolidones and polyvinylimidazoles or mixtures thereof When present in a subject composition, the dye transfer inhibiting agents may be present at levels from about 0.0001% to about 10%, from about 0.01% to about 5% or even from about 0.1% to about 3% by weight of the composition.
Brighteners—The cleaning compositions of the present invention can also contain additional components that may tint articles being cleaned, such as fluorescent brighteners. Suitable fluorescent brightener levels include lower levels of from about 0.01, from about 0.05, from about 0.1 or even from about 0.2 wt % to upper levels of 0.5 or even 0.75 wt %.
Dispersants—The compositions of the present invention can also contain dispersants. Suitable water-soluble organic materials include the homo- or co-polymeric acids or their salts, in which the polycarboxylic acid comprises at least two carboxyl radicals separated from each other by not more than two carbon atoms.
Enzymes—The cleaning compositions can comprise one or more enzymes which provide cleaning performance and/or fabric care benefits. Examples of suitable enzymes include, but are not limited to, hemicellulases, peroxidases, proteases, cellulases, xylanases, lipases, phospholipases, esterases, cutinases, pectinases, mannanases, pectate lyases, keratinases, reductases, oxidases, phenoloxidases, lipoxygenases, ligninases, pullulanases, tannases, pentosanases, malanases, β-glucanases, arabinosidases, hyaluronidase, chondroitinase, laccase, and amylases, or mixtures thereof A typical combination is an enzyme cocktail that may comprise, for example, a protease and lipase in conjunction with amylase. When present in a cleaning composition, the aforementioned additional enzymes may be present at levels from about 0.00001% to about 2%, from about 0.0001% to about 1% or even from about 0.001% to about 0.5% enzyme protein by weight of the composition.
Enzyme Stabilizers—Enzymes for use in detergents can be stabilized by various techniques. The enzymes employed herein can be stabilized by the presence of water-soluble sources of calcium and/or magnesium ions in the finished compositions that provide such ions to the enzymes. In case of aqueous compositions comprising protease, a reversible protease inhibitor, such as a boron compound, can be added to further improve stability.
Catalytic Metal Complexes—Applicants' cleaning compositions may include catalytic metal complexes. One type of metal-containing bleach catalyst is a catalyst system comprising a transition metal cation of defined bleach catalytic activity, such as copper, iron, titanium, ruthenium, tungsten, molybdenum, or manganese cations, an auxiliary metal cation having little or no bleach catalytic activity, such as zinc or aluminum cations, and a sequestrate having defined stability constants for the catalytic and auxiliary metal cations, particularly ethylenediaminetetraacetic acid, ethylenediaminetetra(methylenephosphonic acid) and water-soluble salts thereof. Such catalysts are disclosed in U.S. Pat. No. 4,430,243.
If desired, the compositions herein can be catalyzed by means of a manganese compound. Such compounds and levels of use are well known in the art and include, for example, the manganese-based catalysts disclosed in U.S. Pat. No. 5,576,282.
Cobalt bleach catalysts useful herein are known, and are described, for example, in U.S. Pat. No. 5,597,936; U.S. Pat. No. 5,595,967. Such cobalt catalysts are readily prepared by known procedures, such as taught for example in U.S. Pat. No. 5,597,936, and U.S. Pat. No. 5,595,967.
Compositions herein may also suitably include a transition metal complex of ligands such as bispidones (WO 05/042532 A1) and/or macropolycyclic rigid ligands—abbreviated as “MRLs”. As a practical matter, and not by way of limitation, the compositions and processes herein can be adjusted to provide on the order of at least one part per hundred million of the active MRL species in the aqueous washing medium, and will typically provide from about 0.005 ppm to about 25 ppm, from about 0.05 ppm to about 10 ppm, or even from about 0.1 ppm to about 5 ppm, of the MRL in the wash liquor.
Suitable transition-metals in the instant transition-metal bleach catalyst include, for example, manganese, iron and chromium. Suitable MRLs include 5,12-diethyl-1,5,8,12-tetraazabicyclo[6.6.2]hexadecane.
Suitable transition metal MRLs are readily prepared by known procedures, such as taught for example in WO 00/32601, and U.S. Pat. No. 6,225,464.
Solvents—Suitable solvents include water and other solvents such as lipophilic fluids. Examples of suitable lipophilic fluids include siloxanes, other silicones, hydrocarbons, glycol ethers, glycerine derivatives such as glycerine ethers, perfluorinated amines, perfluorinated and hydrofluoroether solvents, low-volatility nonfluorinated organic solvents, diol solvents, other environmentally-friendly solvents and mixtures thereof.

Processes of Making Compositions

The compositions of the present invention can be formulated into any suitable form and prepared by any process chosen by the formulator, non-limiting examples of which are described in Applicants' examples and in U.S. Pat. No. 4,990,280; U.S. 20030087791A1; U.S. 20030087790A1; U.S. 20050003983A1, U.S. 20040048764A; U.S. Pat. No. 4,762,636; U.S. Pat. No. 6,291,412; U.S. 20050227891A1; EP 1070115A2; U.S. Pat. No. 5,879,584; U.S. Pat. No. 5,691,297; U.S. Pat. No. 5,574,005; U.S. Pat. No. 5,569,645; U.S. Pat. No. 5,565,422; U.S. Pat. No. 5,516,448; U.S. Pat. No. 5,489,392; U.S. Pat. No. 5,486,303 all of which are incorporated herein by reference.

Method of Use

The present invention includes a method for cleaning and/or treating a situs inter alia a fabric surface. Such method includes the steps of contacting an embodiment of Applicants' cleaning composition, in neat form or diluted in a wash liquor, with at least a portion of a fabric surface then optionally rinsing such fabric surface. The fabric surface may be subjected to a washing step prior to the aforementioned rinsing step. For purposes of the present invention, washing includes but is not limited to, scrubbing, and mechanical agitation. Accordingly, the present invention includes a method for laundering a fabric. The method comprises the steps of contacting a fabric to be laundered with a said cleaning laundry solution comprising at least one embodiment of Applicants' composition. The fabric may comprise most any fabric capable of being laundered in normal consumer use conditions. The solution preferably has a pH of from about 7 to about 11. The compositions may be employed at concentrations of from about 500 ppm to about 15,000 ppm in solution. The water temperatures typically range from about 5° C. to about 90° C. The water to fabric ratio is typically from about 1:1 to about 30:1.

Test Method 1

A protocol to define whether a dye or pigment material is a fabric hueing agent for the purpose of the invention is given here:

- 1.) Fill two tergotometer pots with 800 ml of Newcastle upon Tyne, UK, City Water (˜12 grains per US gallon total hardness, supplied by Northumbrian Water, Pity Me, Durham, Co. Durham, UK).
- 2) Insert pots into tergotometer, with water temperature controlled at 30° C. and agitation set at 40 rpm for the duration of the experiment.
- 3) Add 4.8 g of IEC-B detergent (IEC 60456 Washing Machine Reference Base Detergent Type B), supplied by wfk, Brüggen-Bracht, Germany, to each pot.
- 4) After two minutes, add 2.0 mg active colorant to the first pot.
- 5) After one minute, add 50 g of flat cotton vest (supplied by Warwick Equest, Consett, County Durham, UK), cut into 5 cm×5 cm swatches, to each pot.
- 6) After 10 minutes, drain the pots and re-fill with cold Water (16° C.) having a water hardness of 14.4 English Clark Degrees Hardness with a 3:1 Calcium to Magnesium molar ratio.
- 7) After 2 minutes rinsing, remove fabrics.
- 8) Repeat steps 3-7 for a further three cycles using the same treatments.
- 9) Collect and line dry the fabrics indoors for 12 hours.
- 10) Analyse the swatches using a Hunter Miniscan spectrometer fitted with D65 illuminant and UVA cutting filter, to obtain Hunter a (red-green axis) and Hunter b (yellow-blue axis) values.
- 11) Average the Hunter a and Hunter b values for each set of fabrics. If the fabrics treated with colorant under assessment show an average difference in hue of greater than 0.2 units on either the a axis or b axis, it is deemed to be a fabric hueing agent for the purpose of the invention.

EXAMPLE

Examples 1-8

Liquid laundry detergent compositions suitable for front-loading automatic washing machines.


	Composition
	(wt % of composition)

Ingredient	1	2	3	4	5	6	7	8

Alkylbenzene sulfonic acid	7	11	4.5	1.2	1.5	12.5	5.2	4
Sodium C_12-14alkyl ethoxy 3	2.3	3.5	4.5	4.5	7	18	1.8	2
sulfate
C_14-15alkyl 8-ethoxylate	5	8	2.5	2.6	4.5	4	3.7	2
C₁₂alkyl dimethyl amine oxide	—	—	0.2	—	—	—	—	—
C_12-14alkyl hydroxyethyl dimethyl	—	—	—	0.5	—	—	—	—
ammonium chloride
C_12-18Fatty acid	2.6	4	4	2.6	2.8	11	2.6	1.5
Citric acid	2.6	3	1.5	2	2.5	3.5	2.6	2
Protease (Purafect ® Prime)	0.5	0.7	0.6	0.3	0.5	2	0.5	0.6
Amylase (Natalase ®)	0.1	0.2	0.15	—	0.05	0.5	0.1	0.2
Mannanase (Mannaway ®)	0.05	0.1	0.05	—	—	0.1	0.04	—
Xyloglucanase XYG1006*	1	4	3	3	2	8	2.5	4
(mg aep/100 g detergent)
Random graft co-polymer¹	1	0.2	1	0.4	0.5	2.7	0.3	1
A compound having the following	0.4	2	0.4	0.6	1.5	1.8	0.7	0.3
general structure:
bis((C₂H₅O)(C₂H₄O)n)(CH₃)—N⁺—C_xH_2x—N⁺—(CH₃)-
bis((C₂H₅O)(C₂H₄O)n),
wherein n =
from 20 to 30, and x = from 3 to
8, or sulphated or sulphonated
variants thereof
Ethoxylated Polyethylenimine²	—	—	—	—	—	0.5	—	—
Amphiphilic alkoxylated grease	0.1	0.2	0.1	0.2	0.3	0.3	0.2	0.3
cleaning polymer³
Diethoxylated poly (1,2 propylene	—	—	—	—	—	—	0.3	—
terephthalate short block soil
release polymer.
Diethylenetriaminepenta(methylene	0.2	0.3	—	—	0.2	—	0.2	0.3
phosphonic) acid
Hydroxyethane diphosphonic acid	—	—	0.45	—	—	1.5	—	0.1
FWA	0.1	0.2	0.1	—	—	0.2	0.05	0.1
Solvents (1,2 propanediol,	3	4	1.5	1.5	2	4.3	2	1.5
ethanol), stabilizers
Hydrogenated castor oil derivative	0.4	0.4	0.3	0.1	0.3	—	0.4	0.5
structurant
Boric acid	1.5	2.5	2	1.5	1.5	0.5	1.5	1.5
Na formate	—	—	—	1	—	—	—	—
Reversible protease inhibitor⁴	—	—	0.002	—	—	—	—	—
Perfume	0.5	0.7	0.5	0.5	0.8	1.5	0.5	0.8
Perfume MicroCapsules slurry	0.2	0.3	0.7	0.2	0.05	0.4	0.9	0.7
(30% am)
Ethoxylated thiophene Hueing	0.005	0.007	0.010	0.008	0.008	0.007	0.007	0.008
Dye⁵

Buffers (sodium hydroxide,	To pH 8.2
Monoethanolamine)
Water and minors (antifoam,	To 100%
aesthetics)

Examples 9-16

Liquid laundry detergent compositions suitable for top-loading automatic washing machines.


	Composition
	(wt % of composition)

Ingredient	9	10	11	12	13	14	15	16

C_12-15	20.1	15.1	20.0	15.1	13.7	16.7	10.0	9.9
Alkylethoxy(1.8)sulfate
C_11.8Alkylbenzene sulfonate	2.7	2.0	1.0	2.0	5.5	5.6	3.0	3.9
C_16-17Branched alkyl sulfate	6.5	4.9		4.9	3.0	9.0	2.0
C_12-14Alkyl-9-ethoxylate	0.8	0.8	0.8	0.8	8.0	1.5	0.3	11.5
C₁₂dimethylamine oxide			0.9
Citric acid	3.8	3.8	3.8	3.8	3.5	3.5	2.0	2.1
C_12-18fatty acid	2.0	1.5	2.0	1.5	4.5	2.3		0.9
Protease (Purafect ® Prime)	1.5	1.5	0.5	1.5	1.0	1.8	0.5	0.5
Amylase (Natalase ®)	0.3	0.3	0.3	0.3	0.2	0.4
Amylase (Stainzyme ®)								1.1
Mannanase (Mannaway ®)	0.1					0.1
Pectate Lyase (Pectawash ®)	0.1					0.2
Xyloglucanase XYG1006*	5	13	2	5	20	1	2	3
(mg aep/100 g detergent)
Borax	3.0	3.0			2.0	3.0	3.0	3.3
Na & Ca formate	0.2	0.2		0.2	0.2		0.7
A compound having the	1.6	1.6	3.0	1.6	2.0	1.6	1.3	1.2
following general structure:
bis((C₂H₅O)(C₂H₄O)n)(CH₃)—N⁺—C_xH_2x—N⁺—(CH₃)-
bis((C₂H₅O)(C₂H₄O)n),
wherein n = from 20 to 30,
and x = from 3 to 8, or
sulphated or sulphonated
variants thereof
Random graft co-polymer¹	0.4	0.2	1.0	0.5	0.6	1.0	0.8	1.0
Diethylene triamine	0.4	0.4	0.4	0.4	0.2	0.3	0.8
pentaacetic acid
Tinopal AMS-GX	0.2	0.2	0.2	0.2	0.2	0.3	0.1
Tinopal CBS-X						0.1		0.2
Amphiphilic alkoxylated	1.0	1.3	1.3	1.4	1.0	1.1	1.0	1.0
grease cleaning polymer³
Texcare 240N (Clariant)				1.0
Ethanol	2.6	2.6	2.6	2.6	1.8	3.0	1.3
Propylene Glycol	4.6	4.6	4.6	4.6	3.0	4.0	2.5
Diethylene glycol	3.0	3.0	3.0	3.0	3.0	2.7	3.6
Polyethylene glycol	0.2	0.2	0.2	0.2	0.1	0.3	0.1	1.4
Monoethanolamine	2.7	2.7	2.7	2.7	4.7	3.3	1.7	0.4
Triethanolamine								0.9
NaOH	to pH	to pH	to pH	to pH	to pH	to pH	to pH	to pH
	8.3	8.3	8.3	8.3	8.3	8.3	8.3	8.5
Suds suppressor
Dye	0.01	0.01	0.01		0.01	0.01	0.01	0.0
Perfume	0.5	0.5	0.5	0.5	0.7	0.7	0.8	0.6
Perfume MicroCapsules	0.2	0.5	0.2	0.3	0.1	0.3	0.9	1.0
slurry (30% am)
Ethoxylated thiophene	0.003	0.002	0.002	0.005	0.002	0.004	0.004	0.003
Hueing Dye⁵
Water	balance	balance	balance	balance	balance	balance	balance	balance

Examples 17-22

The following are granular detergent compositions produced in accordance with the invention suitable for laundering fabrics.


17	18	19	20	21	22

Linear alkylbenzenesulfonate	15	12	20	10	12	13
with aliphatic carbon chain
length C₁₁-C₁₂
Other surfactants	1.6	1.2	1.9	3.2	0.5	1.2
Phosphate builder(s)	2	25	4	3	2
Zeolite		1		1	4	1
Silicate	4	5	2	3	3	5
Sodium Carbonate	9	20	10	17	5	23
Polyacrylate (MW 4500)	1	0.6	1	1	1.5	1
Carboxymethyl cellulose	1	—	0.3	—	1.1	—
(Finnfix BDA ex CPKelco)
Xyloglucanase XYG1006*	1.5	2.4	1.7	0.9	5.3	2.3
(mg aep/100 g detergent)
Other enzymes powders	0.23	0.17	0.5	0.2	0.2	0.6
Fluorescent Brightener(s)	0.16	0.06	0.16	0.18	0.16	0.16
Diethylenetriamine pentaacetic	0.6		0.6	0.25	0.6	0.6
acid or Ethylene diamine
tetraacetic acid
MgSO₄	1	1	1	0.5	1	1
Bleach(es) and Bleach	6.88		6.12	2.09	1.17	4.66
activator(s)
Ethoxylated thiophene Hueing	0.002	0.001	0.003	0.003	—	—
Dye⁵
Direct Violet 9 ex Ciba Specialty				0.0006	0.0004	0.0006
Chemicals

Sulfate/Moisture/perfume	Balance to 100%

Examples 23-28


23	24	25	26	27	28

Linear alkylbenzenesulfonate	8	7.1	7	6.5	7.5	7.5
with aliphatic carbon chain
length C₁₁-C₁₂
Other surfactants	2.95	5.74	4.18	6.18	4	4
Layered silicate	2.0	—	2.0	—	—	—
Zeolite	7	—	2	—	2	2
Citric Acid	3	5	3	4	2.5	3
Sodium Carbonate	15	20	14	20	23	23
Silicate	0.08	—	0.11	—	—	—
Soil release agent	0.75	0.72	0.71	0.72	—	—
Acrylic Acid/Maleic Acid Copolymer	1.1	3.7	1.0	3.7	2.6	3.8
Carboxymethyl cellulose	0.15	—	0.2	—	1	—
(Finnfix BDA ex CPKelco)
Xyloglucanase XYG1006*	3.1	2.34	3.12	4.68	3.52	7.52
(mg aep/100 g detergent)
Other enzyme powders	0.65	0.75	0.7	0.27	0.47	0.48
Bleach(es) and bleach activator(s)	16.6	17.2	16.6	17.2	18.2	15.4
Azo-CMC ex Megazyme, Ireland	0.1			0.15	0.12	0.44
Ethoxylated thiophene Hueing Dye⁵		0.003	0.003

Sulfate/Water & Miscellaneous	Balance to 100%

¹Random graft copolymer is a polyvinyl acetate grafted polyethylene oxide copolymer having a

polyethylene oxide backbone and multiple polyvinyl acetate side chains. The molecular weight

of the polyethylene oxide backbone is about 6000 and the weight ratio of the polyethylene oxide

to polyvinyl acetate is about 40 to 60 and no more than 1 grafting point per 50 ethylene oxide

units.

²Polyethylenimine (MW = 600) with 20 ethoxylate groups per —NH.

³Amphiphilic alkoxylated grease cleaning polymer is a polyethylenimine (MW = 600) with 24

ethoxylate groups per —NH and 16 propoxylate groups per —NH

⁴Reversible Protease inhibitor of structure:

⁵Ethoxylated thiophene Hueing Dye is as described in U.S. Pat. No. 7,208,459 B2.

*Remark: all enzyme levels expressed as % enzyme raw material, except for xyloglucanase

where the level is given in mg active enzyme protein per 100 g of detergent. XYG1006 enzyme

is according to SEQ ID: 1.

The dimensions and values disclosed herein are not to be understood as being strictly limited to the exact numerical values recited. Instead, unless otherwise specified, each such dimension is intended to mean both the recited value and a functionally equivalent range surrounding that value. For example, a dimension disclosed as “40 mm” is intended to mean “about 40 mm”.
Every document cited herein, including any cross referenced or related patent or application, is hereby incorporated herein by reference in its entirety unless expressly excluded or otherwise limited. The citation of any document is not an admission that it is prior art with respect to any invention disclosed or claimed herein or that it alone, or in any combination with any other reference or references, teaches, suggests or discloses any such invention . Further, to the extent that any meaning or definition of a term in this document conflicts with any meaning or definition of the same term in a document incorporated by reference, the meaning or definition assigned to that term in this document shall govern.
While particular embodiments of the present invention have been illustrated and described, it would be obvious to those skilled in the art that various other changes and modifications can be made without departing from the spirit and scope of the invention. It is therefore intended to cover in the appended claims all such changes and modifications that are within the scope of this invention.

Claims

1. A laundry detergent composition comprising:

(a) a glycosyl hydrolase having enzymatic activity towards both xyloglucan and amorphous cellulose substrates, wherein the glycosyl hydrolase is selected from GH families 5, 12, 44 or 74; and

(b) a fabric hueing agent, said fabric hueing agent being selected from the group consisting of dyes, dye-clay conjugates, and mixtures thereof; and

(c) a detersive surfactant.

2. A composition according to claim 1, wherein said glycosyl hydrolase is present at a level of from 0.0005% to 0.1% and said fabric hueing agent is present at a level of from 0.00003% to 0.1%.

3. A composition according to claim 1, wherein the glycosyl hydrolase enzyme belongs to glycosyl hydrolase family 44.

4. A composition according to claim 1, wherein the glycosyl hydrolase enzyme has a sequence at least 80% homologous to sequence ID No. 1.

5. A composition according to claim 1, wherein the composition is in the form of a liquid.

6. A composition according to claim 1, wherein said dyes are selected from the group consisting of small molecule dyes, polymeric dyes, and mixtures thereof, and said dye-clay conjugates are selected from the group consisting of dye clay conjugates comprising at least one cationic/basic dye and a smectite clay, and mixtures thereof.

7. A composition according to claim 1, wherein said dyes arc selected from the group consisting of small molecule dyes, polymeric dyes, and mixtures thereof, and said dye-clay conjugates are selected from the group consisting of dye clay conjugates comprising at least one cationicibasic dye and a smectite clay, and mixtures thereof.

8. A composition according to claim 1, wherein said small molecule dyes are selected from the group consisting of Direct Violet 9, Direct Violet 35, Direct Violet 48, Direct Violet 51, Direct Violet 66, Direct Blue 1, Direct Blue 71, Direct Blue 80, Direct Blue 279, Acid Red 17, Acid Red 73, Acid Red 88, Acid Red 150, Acid Violet 15, Acid Violet 17, Acid Violet 24, Acid Violet 43, Acid Red 52, Acid Violet 49, Acid Blue 15, Acid Blue 17, Acid Blue 25, Acid Blue 29, Acid Blue 40, Acid Blue 45, Acid Blue 75, Acid Blue 80, Acid Blue 83, Acid Blue 90 and Acid Blue 113, Acid Black 1, Basic Violet 1, Basic Violet 3, Basic Violet 4, Basic Violet 10, Basic Violet 35, Basic Blue 3, Basic Blue 16, Basic Blue 22, Basic Blue 47, Basic Blue 66, Basic Blue 75, Basic Blue 159 and mixtures thereof, said polymeric dyes are selected from the group consisting of polymers containing conjugated chromogens, polymers with chromogens co-polymerised into the backbone of the polymer and mixtures thereof, said dye-clay conjugates are selected from dye clay conjugates comprising a dye selected from the group consisting of C.I. Basic Yellow 1 through 108, C.I. Basic Orange 1 through 69, C.I. Basic Red 1 through 118, C.I. Basic Violet 1 through 51, C.I. Basic Blue 1 through 164, C.I. Basic Green 1 through 14, C.I. Basic Brown 1 through 23, CI Basic Black 1 through 11. and a clay selected from the group consisting of Montmorillonite clay, Hectorite clay, Saponite clay and mixtures thereof.

9. A composition according to claim 1, wherein the small molecule dye is selected from the group consisting of Acid Violet 17, Acid Violet 43, Acid Red 52, Acid Red 73, Acid Red 88, Acid Red 150, Acid Blue 25, Acid Blue 29, Acid Blue 45, Acid Blue 113, Acid Black 1, Direct Blue 1, Direct Blue 71, Direct Violet 51, and mixtures thereof.

10. A composition according to claim 1, wherein the small molecule dye is selected from the group consisting of: Basic Violet 1; Basic Violet 3; Basic Violet 4; Basic Violet 10; Basic Violet 35; Basic Blue 3; Basic Blue 16; Basic Blue 22; Basic Blue 47; Basic Blue 66; Basic Blue 75; Basic Blue 159 and mixtures thereof.

11. A composition according to claim 1, wherein the hueing agent comprises an alkoxylated triphenyl-methane and/or an alkoxylated thiophene polymeric colourant